(t, J = 9.9 Hz, 1 H), 3.00–2.96 (m, 1 H), 2.73 (d, J = 6.3 Hz, 1 H),
1.94–1.82 (m, 2 H), 1.52–1.26 (m, 32 H), 0.88 (t, J = 6.9 Hz,
3 H). 13C NMR (75 MHz, CDCl3): d 170.71, 169.81, 137.64,
132.12, 131.99, 129.79, 129.33, 128.90, 127.14, 125.82, 109.46,
57.29, 39.72, 36.40, 31.91, 29.69, 29.64, 29.63, 29.54, 29.43, 29.35,
29.12, 28.88, 28.19, 22.68, 14.11. IR (KBr) v (cm-1): 3200, 2920,
2850, 1603, 1591, 1573, 1507, 1488, 1450, 1285, 1238, 1077, 1062,
1025, 833, 779, 771, 702. C35H52Cl3NOSTi (689.08): calcd C 61.00,
H 7.61, N 2.03. Found C 60.59, H 7.46, N 1.83.
1452, 1408, 1337, 1284, 1236, 1186, 1120, 1060, 1018, 843, 810.
C22H26Cl3NOSTi (506.74): calcd C 52.14, H 5.17, N 2.76. Found
C 51.50, H 5.22, N 3.23.
[(1Z,3Z) - 1,3 - bis(4 - methoxyphenyl) - 3 - (2 - (propylthio)ethyl
imino)prop-1-en-1-olate]Ti(IV)Cl3 (5i). The same procedure as
1
that for the preparation of 5a was used. Yield: 1.31 g (94%). H
NMR (300 MHz, CDCl3): d 7.78 (d, J = 8.4 Hz, 2 H), 7.23 (d, J
= 8.4 Hz, 2 H), 7.00 (d, J = 8.4 Hz, 2 H), 6.90 (d, J = 8.4 Hz, 2
H), 6.30 (s, 1 H), 4.09 (brs, 2 H), 3.87 (s, 3 H), 3.85 (s, 3 H), 3.41
(brs, 1 H), 3.19 (brs, 1 H), 2.96 (s, 1 H), 2.75 (d, 1 H), 1.96–1.91
(m, 2 H), 1.12 (t, J = 7.5 Hz, 3 H). 13C NMR (75 MHz, CDCl3):
d 163.77, 162.61, 155.81, 153.58, 122.71, 122.19, 121.19, 120.74,
117.50, 107.56, 107.32, 101.59, 50.29, 48.51, 48.47, 34.49, 29.53,
14.78, 6.54. IR (KBr) v (cm-1): 3202, 2839, 1669, 1603, 1589, 1566,
1508, 1478, 1438, 1420, 1336, 1302, 1258, 1240, 1175, 1124, 1060,
1026, 917, 846, 811, 784. C22H26Cl3NO3STi (538.74): calcd C 49.05,
H 4.86, N 2.60. Found C 48.32, H 5.03, N 3.26.
[(1Z,3Z)-1,3-diphenyl-3-(2-(phenylthio)ethylimino)prop-1-en-
1-olate]Ti(IV)Cl3 (5e). The same procedure as that for the prepa-
1
ration of 5b. Yield: (0.31 g, 50%). H NMR (400 MHz, CDCl3,
toluene): d 7.81–7.16 (m, 18 H), 6.40 (s, 1 H), 4.25 (s, 2 H), 3.49
(t, J = 4.8 Hz, 2 H), 2.35 (s, 1.7 H). 13C NMR (100 MHz, CDCl3,
toluene): d 171.01, 170.11, 137.49, 132.81, 132.06, 131.95, 129.92,
129.40, 129.31, 129.02, 128.93, 128.49, 128.20, 127.45, 127.16,
125.86, 125.28, 109.61, 57.50, 35.04, 21.45. IR (KBr) v (cm-1):
3212, 1686, 1588, 1572, 1501, 1483, 1450, 1440, 1282, 1236, 1062,
1026, 766, 742, 698, 687. C23H20Cl3NOSTi(510.98): calcd C 53.88,
H 3.93, N 2.73. Found C 53.68, H 4.19, N 2.20.
[(1Z,3E)-2-benzyl-1,3-diphenyl-3-(2-(propylthio)ethylimino)
prop-1-en-1-olate]Ti(IV)Cl3 (5j). The same procedure as that for
[(1Z,3E) - 1 - phenyl - 3 - (2 - (propylthio)ethylimino)but - 1- en - 1-
olate]Ti(IV)Cl3 (5f). The same procedure as that for the prepara-
tion of 5a. Yield: 1.32 g (79%). 1H NMR (400 MHz, CDCl3): d 7.83
(d, J = 7.6 Hz, 2 H), 7.49–7.41 (m, 3 H), 6.34 (m, 1 H), 4.20 (d, J
= 4.2 Hz, 2 H), 3.42–3.33 (d, 2 H), 2.97–2.91 (d, 2 H), 2.31 (s, 3 H),
1.97–1.93 (m, 2 H), 1.15 (t, J = 7.6 Hz, 3 H). 13C NMR (100 MHz,
CDCl3): d 169.07, 169.02, 132.06, 131.81, 128.96, 128.92, 126.98,
110.10, 55.07, 41.44, 35.93, 23.79, 21.74, 13.53. IR (KBr) v (cm-1):
2964, 1598, 1575, 1504, 1487, 1447, 1408, 1336, 1274, 1243, 1183,
1101, 1075, 1028, 924, 769, 688. C15H20Cl3NOSTi (416.62): calcd
C 43.24, H 4.84, N 3.36. Found C 42.79, H 5.08, N 3.44.
1
the preparation of 5b. Yield: 0.73 g (59%). H NMR (400 MHz,
CDCl3): d 7.58–6.59 (m, 15 H), 3.98 (brs, 1 H), 3.83–3.71 (m, 2 H),
3.50–3.40 (m, 2 H), 3.06 (brs, 1 H), 2.92 (brs, 1 H), 2.62 (brs, 1 H),
1.94–1.87 (m, 2 H), 1.11 (t, J = 7.6 Hz, 3 H). 13C NMR (100 MHz,
CDCl3): d 174.35, 171.90, 139.57, 135.89, 134.16, 130.37, 129.01,
128.64, 128.46, 128.30, 128.28, 128.05, 126.19, 125.70, 119.88,
57.93, 41.58, 37.03, 35.59, 21.75, 13.53. IR (KBr) v (cm-1): 2961,
2928, 1599, 1566, 1495, 1468, 1442, 1328, 1262, 1157, 1141, 1072,
811, 699. C27H28Cl3NOSTi (568.81): calcd C 57.01, H 4.96, N 2.46.
Found C 56.70, H 5.02, N 2.23.
[(1Z,3Z) - 1 - phenyl - 3 - (2 - (propylthio)ethylimino) - 3- (4 -
[(1Z,3E)-2-methyl-1,3-diphenyl-3-(2-(propylthio)ethylimino)
prop-1-en-1-olate]Ti(IV)Cl3 (5k). The same procedure as that for
the preparation of 5b. Yield: 0.75 g (66%).1H NMR (400 MHz,
CDCl3): d 7.57–7.42 (m, 8 H), 7.19 (d, J = 6.4 Hz, 2 H), 4.05–3.90
(m, 2 H), 3.40 (brs, 1 H), 3.12 (brs, 1 H), 2.90 (brs, 1 H), 2.66
(brs, 1 H), 1.96–1.87 (m, 2 H), 1.80 (s, 3 H), 1.11 (t, J = 7.2 Hz,
3 H). 13C NMR (100 MHz, CDCl3): d 174.42, 170.12, 137.20,
134.24, 130.35, 129.63, 129.36, 128.97, 128.29, 125.31, 117.55,
58.18, 41.47, 35.84, 21.74, 19.58, 13.52. IR (KBr) v (cm-1): 3220,
2963, 1583, 1570, 1502, 1474, 1440, 1330, 1158, 1073, 1018, 799,
783, 700. C21H24Cl3NOSTi (492.71): calcd C 51.19, H 4.91, N 2.84.
Found C 51.71, H 5.01, 2.56.
(trifluoromethyl)phenyl)prop-1-en-1-olate]Ti(IV)Cl3
(5g). The
same procedure as that for 5a but using the crude product
of diketone 2c and amine 3f. The pure 5g was isolated by
recrystallization from toluene. Yield: 0.20 g (42%). 1H NMR
(300 MHz, CDCl3): d 7.84–7.79 (m, 4 H), 7.52–7.40 (m, 5 H),
6.32 (s, 1 H), 4.15–3.96 (m, 2 H), 3.44–3.42 (m, 1 H), 3.22 (t,
J = 10.2 Hz, 2 H), 2.98–2.96 (m, 1 H), 2.75 (d, J = 13.2 Hz,
1 H), 2.00–1.90 (m, 2 H), 1.14 (t, J = 8.7 Hz, 2 H). 13C NMR
(100 MHz, CDCl3): d 170.54, 169.19, 141.15, 132.33, 132.17,
131.89, 131.84, 129.00, 127.24, 126.49, 126.18 (q, J = 271 Hz),
108.50, 57.30, 41.62, 36.34, 21.75, 13.54. 19F NMR (282 MHz,
CDCl3): d -63.34. IR (KBr) v (cm-1): 3309, 2967, 2937, 1599,
1577, 1515, 1502, 1488, 1455, 1406, 1322, 1159, 1125, 1106, 1072,
1016, 847, 773. C21H21Cl3F3NOSTi (546.68): calcd C 46.14, H
3.87, N 2.56. Found C 46.56, H 4.28, N 2.59.
[(1Z,3Z)-3-((R)-3-methyl-1-(propylthio)butan-2-ylimino)-1,3-
diphenylprop-1-en-1-olate]Ti(IV)Cl3 (5l). The same procedure as
that for the preparation of 5b. Yield: 0.2 g (19%).1H NMR
(300 MHz, CDCl3): d 7.82 (d, J = 7.2 Hz, 2 H), 7.54–7.21 (m,
8 H), 6.36 (s, 1 H), 4.04 (d, J = 9.3 Hz, 2 H), 3.48 (m, 2 H), 3.25
(brs, 1 H), 2.93 (brs, 1 H), 2.54 (brs, 1 H), 1.90–1.86 (m, 2 H), 1.12
(t, J = 7.2 Hz, 3 H), 0.76 (d, J = 5.7 Hz, 6 H). 13C NMR (75 MHz,
CDCl3): d 172.63, 170.00, 139.58, 132.06, 129.56, 129.38, 129.02,
128.86, 127.21, 126.79, 124.51, 109.79, 73.68, 44.07, 40.28, 33.25,
22.21, 20.10, 19.61, 13.51. IR (KBr) v (cm-1): 3309, 2963, 1587,
1569, 1467, 1332, 1282, 1231, 1125, 1063, 1024, 1000, 762, 703,
683. C23H28Cl3NOSTi (520.77): calcd C 53.05, H 5.42, N 2.69.
Found C 53.19, H 5.33, N 2.65.
[(1Z,3Z)-3-(2-(propylthio)ethylimino)-1,3-di-p-tolylprop-1-en-
1-olate]Ti(IV)Cl3 (5h). The same procedure as that for the prepa-
1
ration of 5a was used. Yield: 1.0 g (88%). H NMR (300 MHz,
CDCl3): d 7.70 (d, J = 7.2 Hz, 2 H), 7.32–7.15 (m, 6 H), 6.35 (s,
1 H), 4.13–4.03 (m, 2 H), 3.42 (brs, 1 H), 3.19–3.15 (m, 1 H), 2.94
(brs, 1 H), 2.73 (brs, 1 H), 2.42 (s, 3 H), 2.38 (s, 3 H), 1.96–1.91
(m, 2 H), 1.13 (t, J = 7.5 Hz, 3 H). 13C NMR (75 MHz, CDCl3):
d 171.02, 169.89, 142.79, 140.03, 134.69, 129.86, 129.61, 129.30,
127.14, 125.87, 109.19, 57.31, 41.46, 36.42, 21.75, 21.62, 21.36,
13.52. IR (KBr) v (cm-1): 3212, 2923, 1607, 1588, 1567, 1482,
8952 | Dalton Trans., 2009, 8945–8954
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The Royal Society of Chemistry 2009
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